Lubricating oil additives



Patented June 3, 1952 Gashmam; Bayonne, N. J a'ssignors .tdSt'arld ardroil Development Company," a corporation manate NoDi'awingr sp"neantiiinaienzs;1e48,

nentien relates to: novel :chemicalprodr= wits and to methods of preparing same, and more particularly it relates to the preparation of chemical condensation products. having improvedwax o ify n prop r i p t cularly. for use as p r depressors for waxy mineral lubricating oils.

--It is known that wax modifying agents maybe prepared bycondensation of relatively long chain paraflinic materials such as-chlorinated -paraffiILWaXLOI -olefins :corresponding thereto, with aromatic hydrocarbons such as naphthalene, benzene, toluene, anthracene, 'phenanthrene, mixed-coalitar aromatics, etc.,as: well as hydroxy or: amine derivatives of: such aromatic hydrocarbonse. g'." phenol, cresols, naplithols, aniline,

xylidine, etc.

The condensation of such-materials has-generallysheen ,oarried sout thepresenceof' .a'FriedeLeGrait catalyst-such as aluminum chloride; zinc 'chloride, boron fluoride; etc, preferably in thepresencebf aninert-solvent such as arefine'd' kerosene, tetrachlorethane, dichlorbenzene, etc, and at 'a; temperature ranging "from about :room: temperature-.toabout 1 30.0? F preferably not exceeding-fiabout: .200 '-F., and generally :using' pro-. portions of-about 2ito 5 mols of the chlorwax type oflconstituentz-to hmoli of: the aromatic constituent; ,Eor:exampie,=about:I0 to -20:parts by'weight ofznaphthalene mayrbe. condensed with 100 parts by weightaofwohlorinated parafiin wax having about:,l0,1t'o,o2.(lchlorine, preferably about 12'to 15% chlorine, in the. presence of aboutlOO to1300 parts by; oftarefinedkercsene solvent, and usingabout 1,2110; 3%:by weight. QfaIumlnum chloridezcatalyst::baseda. on. the weight of the chlorinated paraffin wax, starting-the.reactionat room temperature, and. gradually: raising the temperatureoilthe reaction mixture to a final temperature oflabout 909-.E.ffor.about 5 hours. Residual catalyst-may thenv be. hydrolyzed ;and removed by washingawith'water; alcohol; aqueous caustic-soda 01:..dilute hydrochloricqacid; .etc., .settlinganddrawing. off; theresultant sludge, and finally the desired high: molecular weight Fri'ed'el-Craft condensation product is: removed from the reaction mass by distillationzunder reducedpressuresuchas; under vacuum of about l to 50- mm. mercury absoluteepressureror by steam distillation, to a temperature Of-about SOO F. I

lllie distil-lation residue thus-obtained isa wax mod'ifying agent' which is oil-soluble, has arr, aver-- .agamolecularweight of above about l',000,'pref'-" stancepwhen'added in amounts ranging; from;

to 2.0% to a waxyl mineral.lubricatingtoilihauing:

age, where the oilblends are subjected-to: fre-,

quent fluctuations of high and low'temperaturesb these blends have-sometimes been found? :toabe: solid at temperatures substantiallyabove the- ASTM pour point, and these blendsudidinot show as good pour stability, as measured by the-Testv procedure (described in the Oil and GastJournal, June 24-,- 1948) ,as might be desired;- It'risrone of the primary objects of the present invention-to modify those Fried'eI Cr-aft "condensation products insucha way as toproduce pour depressors having improvedpour. stability.

Broadly, the present invention comprises modir I fyirig;;such wax modifiers and -pour depressors. which maybe referred to as, high molecular weight Friedel- Craft condensation products of a long chain aliphatic compound. and'an aromatic compound,,. by Ireacting them with an aromatic sul'f'onyl halide.

\Exampl'es .off suitable. sulfonyl v halogen. coin-w.

pounds which may, be .used jincludetoluehe isulfonyl chloride, xylene sulfonylichloride, anthraquinene ,sulflonyl' chloride, naphthalene sulfonyl chloride,. etc..

The. secondary reaction, i. e., the condensation of the initialmaliphatic aromatic wax imodi fier with the sulfonyl' halide, is brought about. under substantially the same conditions as usediinsth e initial condensation,v i. e., with. the same typei'of Friedel-Craft catalyst, and at substantially'the, same or slightly lower temperature range, and

preferably in the presence ofaninert'solvent, In carrying out the invention, severalalteltnar'.

tive procedures may be used. For instance, the

initial Friedel-Craft condensation reactioxnmay, be completed and the .desired initial high mo,-, lecular weight condensation productseparated by hydrolysis and removal ,of' residual catalyst,

and recovered by distillation under reduced pressure, and then"subsequently--redissolved irr-a suitable inert solvent-andsubjected to the secondary condensation-by adding the desired amount of' reactive aromatic sulfonyl halide, "e. g. benzene sulfonyl chloride, 'and-- a Friedel- Craft'flzatalyst such asa small amount of aluminum chloride.

It has been found advantageous, however; to addithe-sulfonyl halide directly toa-thetotalre'action product of the first condensation prior'to the hydrolysis step, and to continue the reaction under the same conditions, adding additional catalyst it necessary. In this manner it is possible to have only on set of finishing steps, including catalyst hydrolysis and removal, and dis tillation.

The resulting second or final condensation product is found to have not only good pour dedepressing properties as measured by the ASTM pour point test, but also improved pour stability as measured by the Test V procedure referred to above.

The final condensation product of this invention has a molecular weight somewhat higher than that of the initial condensation product, due to the subsequent chemical condensation but it is still soluble in hydrocarbon oils such as waxy mineral lubricating oil and may be used in concentrations ranging from as little as .01% to 5.0%, preferably 0.05% to 1.0% in such waxy or highly paraflinic lubricating oil basestocks. It may also be used in lubricating grease compositions comprising essentially a waxy oil thickened with a suitable grease-forming soap such as calcium stearate, aluminum stearate, or sodium, lithium or other metal stearates, oleates, naphthenates, etc. These sulfonyl derivatives of aliphatic-aromatic pour depressing condensation products may also be used to improve the physical properties of parafiin wax'itself, especially for use in coating paper, etc. and may also be used as a dewaxing aid in the dewaxing of lubricating oil basestocks.

The invention will be better understood from a consideration of the following experimental data.

Example I 35 grams of naphthalene and grams of aluminum chloride were suspended in 75 cc. of o-dichlorbenzene and the temperature adjusted to 110 F. 259 grams of chlorinated wax (14.3% Cl) was then added to the reaction mixtures over a period of 30 minutes. The temperature was then adjusted to 125 F. and maintained thereat for a period of 2 5; hours at which time 200 cc. additional o-dichlorbenzene and lO grams of aluminum chloride were added, followed by 30 grams of benzene sulfonyl chloride added over a period of 30 minutes. After the addition of the benzene sulfonyl chloride the reaction temperature was maintained at 125 F. for a total reactime period of 3 hours. The product was recovered by destroying the aluminum chloride and distillation by fire and steam to 600 F. A yield of 192 grams of product was obtained.

The product obtained as described above was tested for ordinary pour depressant potency by the standard ASTM procedure in two different types of waxy lubricants. The following results were obtained:

Pour point F.

Original oil +30v Original oil +0.05% product "+5 Original oil 0.1% product Original oil 0.125% product The above data indicate that the condensation products of this invention are very effective pour depressors when tested by the standard ASTM pour point procedure, as they are at least as efiective as the initial wax modifiers used.

These new condensation products are, however, unexpectedly far superior to the initial wax modifiers in regard to pour point stability. For example, when the initial and'final condensation 4 products of Example I were tested in a Waxy lube oil basestock for pour stability by the Test V procedure previously referred to, the following data were obtained:

' Solid Point Per Cent Commercial Dcpressant by Test V Depressant in Oil Procedure 1.25 Commercial (ll-Wax +18 Aromatic Product. 1.25 Present Invention l9 sults of the winter field testing are summarized below:

Overall field rating Commercial chlorwax-aromatic polymer 59 Present invention 71 The pour stability rating is the percent of the times the blends are observed to be fluid for the period of observation.

It is not intended that the invention be limited to the specific materials which have been mentioned merely for the sake of illustration but only by the appended claims in which it is intended to claim all novelty inherent in the invention as well as all modifications coming within the scope and spirit of the invention.

What is claimed is:

1. A process which comprises reacting a chlorwax-naphthalene condensation product having a molecular weight of at least 1,000 and having pour depressing properties with benzene sulfonyl chloride in the ratio of about 1 to 50 parts by weight of sulfonyl chloride per parts by weight of chlorowax-naphthalene condensation product in the presence of a Friedel-Crafts catalyst hydrolyzing and removingresidual catalyst and subjecting the reaction product to distillation under reduced pressure up to a temperature of about 600 F. to obtain the desired final condensation product as distillation residue.

2. Process according to claim 1 carried out in the presence of an inert solvent.

3. Process according to claim 1 carried out in the presence of ortho-dichlorbenzene as solvent.

4. A Friedel-Craft condensation product of a benzene sulfonyl halogen compound with a condensation product having a molecular weight of at least 1,000 of a long chain aliphatic compound and an aromatic compound having at least one substituent group thereon, said final condensation product being soluble in waxy mineral lubrieating oils and being substantially non-volatile up to about 600 F. under reduced pressure, and having good pour depressing properties both as measured by the ASTM pour point test and by the Test V procedure for pour stability.

5. A Friedel-Crafts condensation product of benzene sulfonyl chloride with a condensation product having a molecular weight of at least 1,000 of a chlorinated paraffin wax having about 10% to 20% chlorine content with about 10 to 20 parts by weight of naphthalene, said final condensation product being soluble in waxy mineral lubricating oils and being substantially nonvolatile up to about 600 F. under reduced pressure and having good pour depressing properties and by the Test V procedure for pour stability.

6. Composition comprising a major proportion of a lubricating oil basestock and 0.05% to by Weight based on the lubricating oil basestock of a product comprising essentially a benzene sulfonyl halide derivative of a long chain aliphatic-aromatic Friedel-Crafts condensation product having a molecular weight of at least 1,000, said composition having an improved pour point and improved pour stability.

7. Composition comprising a major proportion of a waxy mineral lubricating oil having dissolved therein at least a pour depressing amount of a benzene sulfonyl halide derivative of a Friedel- Craft condensation product of chlorinated paraffin wax with an aromatic compound having at least one substituent group thereon.

8. Composition according to claim 7 in which the pour depressor is a Friedel-Craft condensation product of benzene sulfonyl chloride with a chlorwax-naphthalene condensation product having a molecular weight of at least 1,000 and having pour depressing properties.

6 9. Composition according to claim '7 having a stable pour point by the Test V procedure at least as low as 10 F.

EUGENE LIEBER. EDWARD P. CASHMAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,142,934 Bruson et al Jan. 3, 1939 2,257,969 Loane Oct. 7, 1941 2,368,670 Lincoln et al Feb. 6, 1945 2,369,023 Coward et al Feb. 6, 1945 2,410,885 Lieber Nov. 12, 1946 2,433,853 Lincoln et a1 Jan. 6, 1948 2,483,499 Lieber et al Oct. 4, 1949 OTHER REFERENCES Rec. Travaux Chimiques des Pays, Bas, Boeseken, vol. 33 (1914), pg. 321.

Organic Chemistry of Sulfur, Suter (1944), pgs. 673-675 and 746. 

1. A PROCESS WHICH COMPRISES REACTING A CHLORWAX-NAPHTHALENE CONDENSATION PRODUCT HAVING A MOLECULAR WEIGHT OF AT LEAST 1,000 AND HAVING POUR DEPRESSING PROPERTIES WITH BENZENE SULFONYL CHLORIDE IN THE RATIO OF ABOUT 1 TO 50 PARTS BY WEIGHT OF CHLOROWAX-NAPHTHALNE CONDENSATION WEIGHT OF CHLOROWAX-NAPHTHALENE CONDENSATION PRODUCT IN THE PRESENCE OF A FRIEDEL-CRAFTS CATALYST HYDROLYZING AND REMOVING RESIDUAL CATALYST AND SUBJECTING THE REACTION PRODUCT TO DISTILLATION UNDER REDUCED PRESSURE UP TO A TEMPERATURE OF ABOUT 600*F. TO OBTAIN THE DESIRED FINAL CONDENSATION PRODUCT AS DISTILLATION RESIDUE.
 6. COMPOSITION COMPRISING A MAJOR PROPORTION OF A LUBRICATING OIL BASESTOCK AND 0.05% TO 10% BY WEIGHT BASED ON THE LUBRICATING OIL BASESTOCK OF A PRODUCT COMPRISING ESSENTIALLY A BENZENE SULFONYL HALIDE DERIVATIVE OF A LONG CHAIN ALIPHATIC-AROMATIC FRIEDEL-CRAFTS CONDENSATION PRODUCT HAVING A MOLECULAR WEIGHT OF AT LEAST 1,000, SAID COMPOSITION HAVING AN IMPROVED POUR POINT AND IMPROVED POUR STABILITY. 